JP2011081007A - Ink composition for sensing hydrogen peroxide gas and hydrogen peroxide gas indicator - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a material which can more easily detect an oxidizing gas. <P>SOLUTION: An ink composition for detecting an oxidizing gas contains at least one type of azo dye, methine dye, triarylmethane dye, and thiazine dye. Furthermore, an ink composition for detecting an oxidizing gas contains a cationic surface active agent that is at least one type selected from among an alkyltrimethylammonium salt, an isoquinolinium salt, an imidazolinium salt, and a pyridinium salt. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an oxidizing gas detection ink composition and an oxidizing gas detection indicator.

  Oxidizing gases such as ozone are used for sterilization / disinfection or deodorization in a certain atmosphere such as a hospital operating room, in addition to sterilization / disinfection of foods, instruments and the like. On the other hand, there are gases such as ozone that are extremely toxic and affect the human body. On the other hand, in the photochemical smog forecast, the oxidant concentration in the atmosphere is an important factor. For this reason, various detection methods have been developed in order to monitor these oxidizing gas concentrations. For example, as a method for detecting ozone, discoloration due to the reaction of the following formula (1) is mainly used.

_{2KI + O → I 2 + K} 2 O
As a detection method using this principle, for example, a gas containing ozone is introduced into a potassium iodide solution, and the color change degree proportional to the amount of iodine generated is optically measured by a colorimeter, or a simple type Conventionally, a method using a detection tube is known.

  However, in the above optical detection method, the measurement method is complicated, and it takes a certain amount of time to detect. Moreover, since the apparatus itself is very expensive, especially when trying to measure the ozone concentration at a plurality of locations simultaneously, a plurality of apparatuses are required, which is very expensive. The detection tube is simpler than the optical method described above, but is still expensive, and it is necessary to suck the oxidant manually or automatically each time it is measured.

  Therefore, the main object of the present invention is to provide a material capable of detecting an oxidizing gas more easily.

  As a result of intensive studies to solve the problems of the prior art, the present inventor has found that the above object can be achieved by employing an ink composition having a specific composition, and has completed the present invention. .

  That is, the present invention relates to the following oxidizing gas detection ink composition and an oxidizing gas detection indicator using the same.

  1. An ink composition for detecting an oxidizing gas, comprising at least one of an azo dye, a methine dye, a triarylmethane dye, and a thiazine dye.

  2. Item 4. The ink composition for detecting an oxidizing gas according to Item 1, further comprising a cationic surfactant.

  3. The ink composition for detecting an oxidizing gas according to claim 2, wherein the cationic surfactant is at least one selected from alkyltrimethylammonium salts, isoquinolinium salts, imidazolinium salts and pyridinium salts.

  4). Item 4. The ink composition for detecting an oxidizing gas according to any one of Items 1 to 3, further comprising at least one of a filler and a resinous binder.

  5). Item 5. The ink composition for detecting an oxidizing gas according to any one of Items 1 to 4, further comprising at least one pigment component that does not change color in an oxidizing gas atmosphere.

  6). The oxidizing gas detection indicator containing the discoloration layer which consists of an ink composition in any one of said claim | item 1 -5.

  7). Item 7. The oxidizing gas detection indicator according to Item 6, further comprising a non-discoloring layer that does not change color in an oxidizing gas atmosphere.

  8). The oxidizing gas detection indicator according to any one of Items 1 to 7, further comprising an anthraquinone dye as the dye.

  The ink composition and indicator of the present invention uses at least one of an azo dye, a methine dye, a triarylmethane dye and a thiazine dye as a detection component, so that the original color does not return after discoloration. It is possible to detect that the oxidizing gas treatment has been performed reliably. It is also possible to freely control the detection sensitivity, the color change rate, and the like by changing the type and blending ratio of the azo dye.

  The ink composition of the present invention can be used as printing, writing, or stamping inks by blending a resin-based binder or the like, and can be used by being applied onto a substrate such as paper or film.

  In the indicator of the present invention, when the non-discoloring layer is formed, the discoloration can be more reliably identified. Further, as a whole configuration, for example, a sheet shape, a plate shape, or the like can be installed anywhere because space is not required and flexibility can be provided by selecting a base material.

  The indicator of the present invention can be used in a wide range of applications because it can represent a design, characters, symbols, etc. according to the purpose of use by appropriately combining the color-changing layer and the non-color-changing layer, and can impart excellent design properties. be able to.

  In particular, when a cationic surfactant is used in the indicator of the present invention, more excellent discoloration can be obtained, and detection with high sensitivity can be realized. By changing the types and blending ratios of the components such as the cationic surfactant and the extender, the detection sensitivity, the color change rate, and the like can be freely controlled, and quantitative measurement can be performed.

<Ink composition for detecting oxidizing gas>
The ink composition for detecting an oxidizing gas of the present invention contains at least one of an azo dye, a methine dye, a triarylmethane dye and a thiazine dye (hereinafter also referred to as “the dye of the present invention”). Features.

The azo dye is not limited as long as it has an azo group —N═N— as a chromophore. Examples thereof include monoazo dyes, polyazo dyes, metal complex azo dyes, stilbene azo dyes, thiazole azo dyes, and the like. More specifically, CIdisperse Red 13
, CIDisperse Red 52, CIDisperse Violet 24, CIDisperse Blue, 44, CIDisper
se Red 58, CI Disperse Red 88, CI Disperse Yellow 23, CI Disperse Orange 1, CI Disperse Orange 5, CISolvent Red 1, CISolvent Red 3, CISolvent Red 23, and the like. These can be used alone or in combination of two or more.

The methine dye may be a dye having a methine group. Therefore, in the present invention, polymethine dyes, cyanine dyes and the like are also included in the methine dyes. These can be appropriately selected from known or commercially available methine dyes. Specifically, CIBasic Red 12, CIBasic Red 13, CIBasic Red 14, CIBasic Red 15, CIBasic Red 27, CIBasic Red 35, CIBasic Red 36, CIBasic Red 37, CIBasic Red 45, CIBasic Red 48, CIBasic Yellow 11, CIBasic Yellow 12, CIBasic Yellow 13, CIBasic Yellow 14, CIBasic Yellow 21, CIBasic Yellow 22, CIBasic Yellow 23, CIBasic Yellow 24, CIBasic Violet 7, CIBasic Violet 15, CIBasic Violet 16, CIBasic Violet 20, CIBasic Violet 21, CIBasic Violet 39 CIBasic Blue 62, CIBasic Blue 63, and the like. These can be used alone or in combination of two or more.

The triarylmethane dye is not limited, and known or commercially available dyes can be used. For example, CIBasic Blue 1, CIBasic Blue 26, CIBasic Blue 5, CIBasic Blue 8, CIBasic Green 1, CIBasic Red 9, CIBasic Violet 12, CIBasic Violet 14, CIBasic Violet 3, CISolvent Green 15, CISolvent Violet 8 it can. These can be used alone or in combination of two or more. Among these triarylmethane dyes, CISolvent Violet 8, CIBasic Green 1, CIBasic Red 9, CIBasic Blue 1, and the like can be suitably used.

The thiazine dye is not particularly limited and can be selected from known or commercially available ones. For example, CIBasic Blue 9, CIBasic Blue 25, CIBasic Blue 24, CIBasic Blue
17, CI Basic Green 5, CISolvent Blue 8, and the like. These can be used alone or in combination of two or more. Among these thiazine dyes, CI Basic Blue 9 and the like can be suitably used.

  The content of the dye of the present invention varies depending on the kind of dye used, desired detection characteristics, and the like, but is 0.01 to 10% by weight in the ink composition, preferably 0.05 to 5% by weight, more preferably 0.00. It may be 1 to 2% by weight.

  In the present invention, a dye or pigment other than the dye of the present invention may coexist. For example, an anthraquinone dye can be used in combination. The anthraquinone dye is not particularly limited as long as it has a basic skeleton of anthraquinone, and known anthraquinone disperse dyes and the like can also be used.

More specifically, for example, 1,4-diaminoanthraquinone (CIDisperse Violet 1)
1-amino-4-hydroxy-2-methoxyanthraquinone (CIDisperse Red 4), 1-amino-4-methylaminoanthraquinone (CIDisperseViolet 4), 1,4-diamino-2-methoxyanthraquinone (CIDisperse Red 11), 1 -Amino-2-methylanthraquinone (CIDisperse Orange 11), 1-amino-4-hydroxyanthraquinone (CIDisperse Red 15), 1,4,5,8-tetraaminoanthraquinone (CIDisperse Blue 1), 1,4-diamino- 5-Nitroanthraquinone (CIDisperse Violet 8
(The dye number is in parentheses). CISolvent Blue 14, CISolvent Blue 63, CISolvent Violet 13, CISolvent Violet 14, CISolventRed 52, CISolvent Red 114, CIVat Blue 21, CIVat Blue 30, CIVatViolet 15, CIVat Violet 17, CIVat Red 19, CIVat Red 28, CIAcid Blue 23, CIAcid Blue 80, CIAcid Violet 43, CIAcid Violet 48, CIAcid Red 81, CIAcid Red 83,
Dyes known as CI Reactive Blue 4, CI Reactive Blue 19, CI Disperse Blue 7 and the like can also be used. These anthraquinone dyes can be used alone or in combination of two or more. Among these anthraquinone dyes, CI Disperse Blue 7
CI Disperse Violet 1 and the like are preferable. In the present invention, the detection sensitivity can be controlled by changing the type (molecular structure, etc.) of these anthraquinone dyes.

  The content of the anthraquinone dye is not limited, but is preferably 0.01 to 10% by weight, particularly 0.05 to 5% by weight in the ink composition.

  In the present invention, other dyes or pigments may coexist. In particular, a pigment component that does not change color in an oxidizing gas treatment atmosphere (referred to as “non-color-change pigment”) may be included. Thereby, the visual recognition effect can be further enhanced by a change in color tone from one color to another. A known ink (ordinary color ink) can be used as the non-color-changing dye. What is necessary is just to set suitably content of the non-color-change pigment | dye in this case according to the kind etc. of the non-color-change pigment | dye.

  More preferably, the ink composition of the present invention further contains a cationic surfactant.

  The cationic surfactant is not particularly limited, but at least one of alkyl ammonium salt, isoquinolinium salt, imidazolinium salt and pyridinium salt can be used. These may be known or commercially available products. In the present invention, a superior detection sensitivity can be obtained by using these cationic surfactants together with the anthraquinone dye.

  Of the alkylammonium salts, alkyltrimethylammonium salts and dialkyldimethylammonium salts are preferred. Specifically, palm alkyltrimethylammonium chloride, tallow alkyltrimethylammonium chloride, behenyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, lauryltrimethylammonium chloride, octadecyltrimethylammonium chloride, dioctyldimethylammonium chloride, distearyldimethylammonium chloride, chloride Examples thereof include alkylbenzyldimethylammonium. In particular, coconut alkyltrimethylammonium chloride and lauryltrimethylammonium chloride are preferable.

  Examples of the isoquinolinium salt include lauryl isoquinolinium bromide, cetyl isoquinolinium bromide, cetyl isoquinolinium chloride, lauryl isoquinolinium chloride and the like. Among these, lauryl isoquinolinium bromide is particularly preferable.

  Examples of the imidazolinium salt include 1-hydroxyethyl-2-oleylimidazolinium chloride and 2-chloro-1,3-dimethylimidazolinium chloride. Among these, 2-chloro-1,3-dimethylimidazolinium chloride is particularly preferable.

Examples of the pyridinium salt include pyridinium chloride, 1-ethylpyridinium bromide, hexadecylpyridinium chloride, cetylpyridinium chloride, 1-butylpyridinium chloride, Nn-butylpyridinium chloride, hexadecylpyridinium bromide, N-hexadecylpyridinium bromide, 1-dodecylpyridinium chloride, 3-methylhexylpyridinium chloride, 4-methylhexylpyridinium chloride, 3-methyloctylpyridinium chloride, 2-chloro-1-methylpyridinium iodide, 3,4-dimethylbutylpyridinium chloride, pyridinium-n -Hexadecyl chloride-hydrate, N- (cyanomethyl) pyridinium chloride, N-acetonyl pyridi Umbromide, 1- (aminoformylmethyl) pyridinium chloride, 2-amidinopyridinium chloride, 2-aminopyridinium chloride, N-aminopyridinium iodide, 1-aminopyridinium iodide, 1-acetonylpyridinium chloride, N-acetonyl Examples include pyridinium bromide. Among these, hexadecylpyridinium chloride is particularly preferable.

  The content of the cationic surfactant can be changed depending on the kind of the cationic surfactant to be used and the like, but is 0.2 to 30% by weight, particularly 0.5 to 10% by weight in the ink composition of the present invention. preferable.

  In the ink composition of the present invention, components used in known inks such as a resin-based binder, an extender, and a solvent can be appropriately blended as necessary.

  The resin binder may be appropriately selected according to the type of the substrate and the like. For example, known resin components used in ink compositions for writing and printing can be used as they are. Specifically, for example, maleic resin, amide resin, ketone resin, alkylphenol resin, rosin modified resin, polyvinyl butyral, polyvinyl pyrrolidone, cellulose resin, polyester resin, styrene maleic resin, styrene acrylic resin, acrylic resin, etc. Can be mentioned.

  The content of the resin binder can be appropriately set depending on the kind of the resin binder to be used, desired ink characteristics, and the like, but is preferably 50% by weight or less, particularly preferably 5 to 35% by weight in the ink composition of the present invention.

  The extender is not particularly limited, and examples thereof include bentonite, activated clay, aluminum oxide, silica and the like. In addition, materials known as known extender pigments can be used. Among these, a porous thing is preferable and especially a silica is more preferable. By adding such a bulking agent, detection sensitivity can be mainly increased.

  The content of the extender is preferably 1 to 30% by weight, more preferably 2 to 20% by weight in the ink composition of the present invention, although it depends on the type of extender used.

  As the solvent that can be used in the present invention, any solvent that is usually used in ink compositions for printing, writing, etc. can be used. For example, various solvents such as alcohol-based, ester-based, ether-based, ketone-based and hydrocarbon-based solvents can be used, and may be appropriately selected according to the solubility of the dye used and the resin-based binder.

  What is necessary is just to adjust suitably content of a solvent so that it may become the remainder except components other than a solvent from this invention ink composition.

  These components may be blended simultaneously or sequentially and mixed uniformly using a known stirrer such as a homogenizer or a dissolver. For example, the dye of the present invention, if necessary, a cationic surfactant, a resinous binder, an extender and the like may be blended in this order in a solvent and mixed and stirred with a stirrer.

(2) Oxidizing gas detection indicator The oxidizing gas detection indicator of the present invention has a discoloration layer made of the ink composition. In general, the color changing layer can be suitably formed on a substrate.

The substrate is not particularly limited as long as a discoloration layer can be formed. For example, metals / alloys, woody materials, paper, ceramics, glass, concrete, plastics, fibers (nonwoven fabrics, woven fabrics, other fiber sheets), composite materials thereof, and the like can be used.

  The color changing layer in the present invention includes not only the color changing to another color but also the color fading or erasing.

  The discoloration layer can be formed by using the ink composition of the present invention according to a known printing method such as silk screen printing, gravure printing, offset printing, letterpress printing, flexographic printing and the like. It can also be formed by methods other than printing. For example, the discoloration layer can be formed by immersing the substrate in the ink composition. It is particularly suitable for materials into which ink penetrates, such as paper and nonwoven fabric.

  In the present invention, a non-discoloring layer that does not change color in an oxidizing gas atmosphere may be formed on the substrate and / or the discoloring layer. The non-discoloring layer can be usually formed with a commercially available ordinary color ink. For example, water-based ink, oil-based ink, solventless ink, and the like can be used. The ink used for forming the non-discoloring layer may contain components blended in a known ink, such as a resin-based binder, an extender, and a solvent.

  The non-discoloring layer may be formed in the same manner as in the discoloring layer. For example, normal color ink can be used according to a known printing method such as silk screen printing, gravure printing, offset printing, letterpress printing, or flexographic printing. The order of printing of the color changing layer and the non-color changing layer is not particularly limited, and may be appropriately selected according to the design to be printed.

  In the indicator of the present invention, one color changing layer and one non-color changing layer may be formed, or a plurality of layers may be formed. Further, discoloration layers or non-discoloration layers may be laminated. In this case, the discoloration layers may have the same composition or different compositions. Similarly, the non-discoloring layers may have the same composition or different compositions.

  Furthermore, the color-changing layer and the non-color-changing layer may be formed on the entire surface of the substrate or each layer, or may be partially formed. In these cases, in particular, in order to ensure the color change of the color change layer, the color change layer and the non-color change layer may be formed so that a part or all of at least one color change layer is exposed to the oxidizing gas treatment atmosphere.

  In the present invention, the discoloration layer and the non-discoloration layer may be combined in any way as long as the completion of the oxidizing gas treatment can be confirmed. For example, a color-changing layer and a non-color-changing layer are formed so that the color difference between the color-changing layer and the non-color-changing layer can be discriminated only after the color-changing layer is changed, or a color difference between the color-changing layer and the non-color-changing layer disappears only after the color change It can also be formed. In the present invention, it is particularly preferable to form the color-changing layer and the non-color-changing layer so that the color difference between the color-changing layer and the non-color-changing layer can be discriminated only by the color change.

  In order to identify the color difference, for example, the color-changing layer and the non-color-changing layer may be formed so that at least one of a character, a pattern, and a symbol appears only when the color-changing layer changes. In the present invention, characters, designs, and symbols include all information that informs discoloration. What is necessary is just to design these characters etc. suitably according to the purpose of use.

  Further, the color changing layer and the non-color changing layer before the color change may be different from each other. For example, they may be substantially the same color so that the color difference (contrast) between the color-change layer and the non-color-change layer can be identified only after the color change.

  In the indicator of the present invention, the color changing layer and the non-color changing layer can be formed so that the color changing layer and the non-color changing layer do not overlap. As a result, the amount of ink used can be saved.

  Furthermore, in the present invention, a color changing layer or a non-color changing layer may be further formed on at least one of the color changing layer and the non-color changing layer. For example, if a color-changing layer having a different design is formed on a layer in which the color-changing layer and the non-color-changing layer are formed so as not to overlap the color-changing layer and the non-color-changing layer (referred to as “color-changing-non-color-changing layer”), Since the boundary line between the color changing layer and the non-color changing layer in the color changing-non-color changing layer can be made substantially indistinguishable, a more excellent design can be achieved.

  The indicator of the present invention can be applied when detecting oxidizing gas. In particular, examples of the oxidizing gas include ozone, hydrogen peroxide, ethylene oxide, and nitrogen oxide. The indicator of the present invention exposed to these gases changes the color of the dye of the present invention by the reaction of the dye of the present invention. Therefore, when using the indicator, for example, the indicator of the present invention may be placed in a commercially available oxidizing gas processing apparatus and exposed to an oxidizing gas atmosphere together with equipment for sterilization, disinfection, etc. using an oxidizing gas. In this case, it can be detected that the treatment with the predetermined oxidizing gas has been performed by the color change of the color change layer of the indicator placed in the apparatus.

  Examples are given below to further clarify the features of the present invention. In addition, this invention is not restrict | limited to the aspect of an Example.

Examples 1-18
Inks were prepared using the components shown in Table 1. More specifically, after stirring and mixing a solvent, a dye and a resin with a dissolver, a non-discoloring pigment (if necessary) and a resin binder are added and further stirred, and a cationic surfactant and an extender are added and mixed. Thus, an ink was obtained.

The details of each component in Table 1 are as follows.
(1) Dye
CIBasic Red 14: Methine dye
CIBasic Violet 7: Azo dye
CIDisperse Orange 13: Azo dye
CIBasic Blue 9: Thiazine dye
CISolvent Violet 8: Triarylmethane dye
CISolvent Blue 14: Anthraquinone dye (2) Non-discoloring dye Microlith Green GT (manufactured by Ciba Specialty Chemicals)
Microlith Yellow 3R-T (manufactured by Ciba Specialty Chemicals)
(3) Resin binder Versamide 756 (manufactured by Cognis Japan, polyamide)
Jonkrill 690 (John Sun Polymer, styrene acrylic resin)
Denka Butyral # 2000-L (manufactured by Denki Kagaku Kogyo, polyvinyl butyral)
Nitrified cotton RS1 / 2 (Daicel Chemical, Nitrocellulose)
(4) Cationic surfactant NIKKOL CA-2150 (manufactured by Nikko Chemicals)
NIKKOL CA-2465 (manufactured by Nikko Chemicals)
Laurylisoquinolinium bromide (Wako Pure Chemical Industries, Ltd., reagent)
2-Chloro-1,3-dimethylimidazolinium chloride (manufactured by Wako Pure Chemical Industries, Ltd., reagent)
Cetylpyridinium chloride (Wako Pure Chemical Industries, Ltd., reagent)
(5) Bulking agent Aerosil R-972 (manufactured by Nippon Aerosil)
(6) Solvent Butyl cellosolve cyclohexanone Test example 1
The ink composition obtained in each example was examined for discoloration by ozone. Each ink composition was printed on a PET film by silk screen printing (350 mesh). The printed matter was exposed to ozone under the condition that the CT value was 1000 ppm · min with an ozone generator. The discoloration of the sample after the treatment was visually observed. The results are shown in Table 1.

Test example 2
The ink composition obtained in each example was examined for discoloration by hydrogen peroxide gas. Each ink composition was printed on a PET film by silk screen printing (350 mesh). A hydrogen peroxide solution was dropped into a sealed container at 40 ° C. under a reduced pressure so as to be 18000 ppm · min, and the printed matter was exposed to the atmosphere. The sample was visually observed for discoloration after exposure. The results are shown in Table 1.

Claims (8)

An ink composition for detecting an oxidizing gas, comprising at least one of an azo dye, a methine dye, a triarylmethane dye, and a thiazine dye. The ink composition for detecting an oxidizing gas according to claim 1, further comprising a cationic surfactant. The ink composition for detecting an oxidizing gas according to claim 2, wherein the cationic surfactant is at least one selected from alkyltrimethylammonium salts, isoquinolinium salts, imidazolinium salts and pyridinium salts. The ink composition for detecting an oxidizing gas according to any one of claims 1 to 3, further comprising at least one of a filler and a resin binder. Furthermore, the ink composition for oxidizing gas detection in any one of Claims 1-4 containing at least 1 sort (s) of the pigment | dye component which does not discolor in oxidizing gas atmosphere. An oxidizing gas detection indicator comprising a discoloration layer comprising the ink composition according to any one of claims 1 to 5. The oxidizing gas detection indicator according to claim 6, further comprising a non-discoloring layer that does not change color in an oxidizing gas atmosphere. Furthermore, the oxidizing gas detection indicator in any one of Claims 1-7 containing an anthraquinone type dye as dye.